EP0524823B1 - Harzzusammensetzung und daraus hergestellte Verpackungsmaterialien für Lebensmittel - Google Patents

Harzzusammensetzung und daraus hergestellte Verpackungsmaterialien für Lebensmittel Download PDF

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Publication number
EP0524823B1
EP0524823B1 EP19920306750 EP92306750A EP0524823B1 EP 0524823 B1 EP0524823 B1 EP 0524823B1 EP 19920306750 EP19920306750 EP 19920306750 EP 92306750 A EP92306750 A EP 92306750A EP 0524823 B1 EP0524823 B1 EP 0524823B1
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EP
European Patent Office
Prior art keywords
oxygen
carbon dioxide
gtr
film
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19920306750
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English (en)
French (fr)
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EP0524823A2 (de
EP0524823A3 (en
Inventor
Kazuhiko Hirose
Nobuyuki Hisazumi
Shinichiro Funabashi
Hiroyuki Ohba
Hideaki Tanaka
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Kureha Corp
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Kureha Corp
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Publication date
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Publication of EP0524823A2 publication Critical patent/EP0524823A2/de
Publication of EP0524823A3 publication Critical patent/EP0524823A3/en
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Publication of EP0524823B1 publication Critical patent/EP0524823B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a resin composition and articles obtained therefrom such as films, and to the use of the articles in packaging food.
  • plastic packaging materials intended for use with, for example, cheese products and coffee beans have a higher gas transmission rate (hereinafter abbreviated to "GTR") to carbon dioxide and a lower GTR to oxygen
  • GTR gas transmission rate
  • Packaging materials that have a low oxygen GTR and a high carbon dioxide/oxygen GTR ratio are desired.
  • the present invention provides a composition which comprises:
  • B 2 is preferably polyethylene glycol.
  • the present invention also provides a melt-extruded article which comprises at least one layer comprising a resin composition as defined above.
  • the melt-extruded article is preferably a food packaging film.
  • the preferred kind of food to be packaged is cheese.
  • the present invention further provides the use of an article as defined above in packaging cheese.
  • Fig. 1 illustrates an apparatus for measuring the solubilities of carbon dioxide and oxygen to organic compounds.
  • the degree of polymerization of the PVA(A) used in the present invention is preferably 300 or higher as measured according to JIS-K6726 in order to produce a strong film and preferably 3500 or lower to facilitate processing and, furthermore, particularly preferably in the range of 500 to 2000. While the degree of saponification of the PVA which is used is within the range of 60 to 95 mole%, it is preferably in the range of 60 to 90 mole%, and more preferably in the range of 60 to 80 mole%.
  • the degree of saponification of PVA of 60 mole% or higher and 95 mole% or lower are both preferable, since the former reduces the oxygen GTR of the obtained film and the latter keeps the saturated solubility of the compound (B 2 ) from being reduced excessively.
  • a PVA having a degree of saponification of 95 mole% or lower is preferable in that it gives a wide temperature differential between the melting point and the thermal decomposition initiating temperature, namely, the processable temperature range.
  • the compound (B 2 ) used in the present invention is an alkylene glycol monomer or polymer thereof and its carbon dioxide/oxygen solubility ratio (SCO 2 /SO 2 ) is 30 or higher, or preferably 50 or higher.
  • alkylene glycol include such monomers as ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol.
  • polyethylene glycol hereinafter abbreviated as "PEG”
  • PEG polyethylene glycol
  • PEG as the preferable polymer, has an average molecular weight of 400 or more for such reason that it is then not readily lost during the film forming step by the melt extrusion technique.
  • the average molecular weight of PEG there is not any particular upper limit for the average molecular weight of PEG.
  • the average molecular weight be about 2000 or less from the viewpoint of miscibility with PVA.
  • the resin composition of the present invention comprises said PVA (A), said composition (B 2 ) and a saponified ethylene/vinyl acetate copolymer resin (hereinafter abbreviated as "EVOH") (C).
  • the compound (B 2 ) is preferably PEG.
  • the PVA (A)/EVOH (C) blending ratio is preferably within the range of 20 to 50 weight % of EVOH to an aggregate of PVA and EVOH, particularly within the range of 30 to 40 weight %. Said blending ratios are desirable because the oxygen GTR is not excessively large as long as EVOH is present at 20% by weight or more and because the carbon dioxide/oxygen GTR ratio is increased if EVOH is present at 50% by weight or less.
  • the lower limit of the blending ratio of the compound (B 2 ) is 3 weight parts per 100 weight parts of PVA, and is preferably 5 weight parts.
  • the carbon dioxide/oxygen GTR ratio of the film is improved by blending the compound (B 2 ) by 3 weight parts or more.
  • the carbon dioxide/oxygen GTR ratio of the film increases with an increase in the blending ratio of the compound (B 2 ).
  • compositions there may be added to said composition, if necessary, various kinds of stabilizers, antiblocking agents, lubricants, colorants and fillers to the extent that they do not impair the effect of the present invention.
  • an example of a preferable method is that PVA impregnated with the compound (B 2 ) with heating at about 60°C is left to stand for several hours to undergo aging and the obtained substance is dry blended with EVOH (C).
  • the compound (B 2 ) used is of a type which is solid at ambient temperature, those three components may be dry blended directly. The mixture is formed into film and the like. It is preferable that a composition pelletized beforehand by a twin-screw extruder or the like be used.
  • the obtained impregnated mixture or pellet is formed into articles such as film, sheet or tray. While melt extrusion is preferable as the forming method, the forming method is not limited thereto alone. In the case of film, which is a particularly preferable formed article, film may be oriented monoaxially or biaxially. Methods such as compression molding, extrusion by T-die, coextrusion by a circular die and deep draw forming may be employed as the forming method. Particularly, in cases where laminated films are formed by combining a core layer made from the composition of the present invention with other kinds of resin as mentioned in the following; methods such as extrusion lamination and coextrusion lamination may be employed.
  • the film is formed so that the core layer will have a thickness of 3 to 50 microns, preferably 5 to 30 microns, although the optimal thickness varies with whether the film produced from the composition of the present invention is used independently, or the film made from the composition of the present invention is used as the core layer for producing a laminate with films made from other kinds of resin.
  • the oxygen GTR of the core layer of the package film comprising the composition of the present invention is 400 cc/m 2 .day.atm. (30°C, dry) or less, preferably 300 cc/m 2 .day.atm. (30° C, dry) or less, and a carbon dioxide/oxygen GTR ratio of 5 or more, preferably 6 or more.
  • the core layer may be used independently as described above, it is particularly preferable with a view to improving the water repellency, heat sealability and securing a practical strength that it is used in the form of a laminate obtained by laminating onto it layers of other kinds of thermoplastic resin.
  • the laminate may be constructed of two layers consisting of the core layer and a layer of another resin, or three or more layers consisting of the core layer and layers of other kinds of thermoplastic resins laminated on both sides of the core layer.
  • the two or more outside layers laminated onto both sides of the core layer may be of the same kind or different kinds of resin, it is preferable that the material of the innermost layer contacting directly to the foods be constructed of a heat sealable resin and the outside layer be constructed of a resin having a reinforcing effect.
  • a type of resin is selected which does not impair the selective gas permeability of the core layer.
  • the laminated thermoplastic layer has an oxygen GTR of 1000 cc/m 2 .day.atm., 30 microns thickness (30°C, dry) or more.
  • thermoplastic resin to be laminated onto the core layer at least one kind of ethylene copolymer wherein its comonomer being selected from among vinyl acetate, and acrylates such as ethyl acrylate, methyl acrylate, and methyl methacrylate, or polyolefin resins such as high pressure process low-density polyethylene, linear low-density polyethylene (L-LDPE), polypropylene, and ionomer, and, furthermore, polyamide resins.
  • An adhesive resin layer may be used for laminating the external layer onto the core layer.
  • the adhesive resin the thermoplastic polymer containing carboxyl group or its derivative, such as polyolefin graft-modified with maleic acid, fumaric acid or maleic anhydride, the resins obtained by copolymerizing those monomers with olefins, and, moreover, adipic acid polyesters having urethane-combined carboxyl group.
  • the film provided by the present invention may be used for packaging foodstuff as a whole, it is particularly suitable for use as packaging material for cheese products such as natural cheese or coffee beans and the like. Particularly, for the use of packaging natural cheese, there is no need to change the packaging throughout the whole step, from the ripening stage to the latter stages of physical distribution.
  • the amount of carbon dioxide generated and the extent of growth of surface molds in the presence of oxygen during the ripening of natural cheese vary with the kind of natural cheese, the kind of live bacteria and conditions of ripening.
  • Four specimens of packaging material having differentiated thicknesses and compositions (the amount of plasticizer) of the core layer were compared with one another with respect to such performances as the swelling of the packaging material due to generation of gas and growth of surface molds during the ripening step, the carbon dioxide GTR, the oxygen GTR and the carbon dioxide/oxygen GTR ratio as opposed to four typical kinds of cheese.
  • Table 1 The result of this study is shown in Table 1.
  • the preferable oxygen GTR is about 400 cc/m 2 .day.atm. or less and the preferable carbon dioxide/oxygen GTR ratio is 5 or more, although there can be few exceptions to this general tendency.
  • the gas transmission rates to both oxygen and carbon dioxide were measured simultaneously at 30°C, using a gas GTR testing apparatus GTR-10A manufactured by Yanagimoto Manufacturing Co.
  • PVA manufactured by Kuraray Co., the degree of saponification of 60 mol%, the degree of polymerization: 500
  • PEG the average molecular weight: 600
  • BT-30, 30 mm diameter twin-screw extruder
  • Results of measurement of the gas GTR, etc. of the obtained film are shown in Table 4. It can be seen from Table 8 that the GTR ratio of this laminated film has increased if the composition of the invention disclosed in the present application is used.
  • a five-layer oriented film (Comparative Example 2) was obtained by the same procedure as employed in Example 1, except that the below-specified weight parts of PVA (manufactured by Kuraray Co., the degree of saponification: 55 mole%, the degree of polymerization: 500) and PEG (the average molecular weight: 600) were mixed together. Results of the measurement of GTR of the obtained ratio are shown in Table 5.
  • Example 2 the same procedure as employed in Example 1 was followed in order to obtain data as Comparative Example 3, except that PVA (the degree of polymerization: 500) having a degree of saponification of 98.5 mole% was used.
  • PVA the degree of polymerization: 500
  • the attempt to melt extrude the mixture ended in failure, as the crystalline melting point of PVA (220°C) is higher than the thermal decomposition initiating temperature (190°C) and said two temperature levels are close to each other.
  • Example 10 Using the 5-layer unoriented film obtained in Example 5 (Example 9) and Example 7 (Example 10), package tests were carried out on two kinds of shred-type cheese.
  • the following two kinds of cheese were used as specimens: "Samsoe”, a produce of Denmark, characterized by a high carbon dioxide generation rate "Maribo”, a produce of Denmark, characterized by a low carbon dioxide generation rate
  • each of the aforementioned cheese was packed in 5 bags, each of which being prepared by heat sealing a piece of film cut out from each kind of the sample packaging material along both sides and one end. After displacing the interior of the bag with a mixture gas consisting of 70% oxygen gas and 30% carbon dioxide gas, the remaining open end of the bag was heat sealed.
  • the size of the packed bag was 140 x 200 mm.
  • the samples thus prepared were stored at 15°C and 68% relative humidity, and after the lapse of given storage periods the packed products were observed with respect to visible growth of surface molds and swelling of the bag.

Claims (5)

  1. Harzzusammensetzung, umfassend:
    i) ein Polyvinylalkoholharz mit einem Verseifungsgrad von 60 bis 95 Mol-% (A);
    ii) ein Alkylenglycol-Monomer oder -Polymer davon mit einem Kohlendioxid/Sauerstoff-Löslichkeitsverhältnis (SCO2/SO2) von 30 oder größer (B2); und
    iii) ein verseiftes Ethylen/Vinylacetat-Copolymerharz (C);
    wobei das Mischungsverhältnis bei B2 3 Gewichtsanteile von B2 zu 100 Gewichtsanteilen von A bis zur gesättigten Löslichkeit von B2 in A und das Mischungsverhältnis bei C von 20 bis 50 Gewichtsanteile von C zu 100 Gewichtsanteilen eines Aggregats von A und C beträgt.
  2. Harzzusammensetzung nach Anspruch 1, wobei B2 Polyethylenglycol ist.
  3. Schmelzextrudierter Gegenstand, der mindestens eine Schicht enthält, umfassend eine Harzzusammensetzung nach Anspruch 1 oder 2.
  4. Schmelzextrudierter Gegenstand nach Anspruch 3, bei dem es sich um einen Nahrungsmittel-Verpackungsfilm handelt.
  5. Verwendung eines Gegenstands nach Anspruch 3 oder 4 zum Verpacken von Käse.
EP19920306750 1991-07-26 1992-07-23 Harzzusammensetzung und daraus hergestellte Verpackungsmaterialien für Lebensmittel Expired - Lifetime EP0524823B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP20889691 1991-07-26
JP66004/91U 1991-07-26
JP6600491 1991-07-26
JP6600491U 1991-07-26
JP208896/91 1991-07-26
JP20889691 1991-07-26

Publications (3)

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EP0524823A2 EP0524823A2 (de) 1993-01-27
EP0524823A3 EP0524823A3 (en) 1993-05-05
EP0524823B1 true EP0524823B1 (de) 1999-10-06

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EP19920306750 Expired - Lifetime EP0524823B1 (de) 1991-07-26 1992-07-23 Harzzusammensetzung und daraus hergestellte Verpackungsmaterialien für Lebensmittel

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US (2) US5270372A (de)
EP (1) EP0524823B1 (de)
AU (1) AU647291B2 (de)
DE (1) DE69230086T2 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5430090A (en) * 1993-02-22 1995-07-04 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Hot-melt adhesive
NL9301996A (nl) * 1993-11-18 1995-06-16 Rudolph Arthur Marinus Kooijma Biologisch afbreekbaar vezelprodukt, werkwijze voor de bereiding hiervan, en voortbrengselen, die uit dit vezelprodukt zijn gevormd.
US5506297A (en) * 1993-12-21 1996-04-09 Kureha Kagaku Kogyo Kabushiki Kaisha Resin composition and melt-extruded article formed therefrom
US5561085A (en) 1994-12-19 1996-10-01 Martin Marietta Corporation Structure for protecting air bridges on semiconductor chips from damage
JPH08283570A (ja) * 1995-04-17 1996-10-29 Sumitomo Chem Co Ltd 樹脂組成物
JPH09316208A (ja) * 1996-03-22 1997-12-09 Kureha Chem Ind Co Ltd 気体選択透過性を有する成形物、そのフイルムおよびその製造方法
KR100220781B1 (ko) * 1996-09-26 1999-09-15 아라끼 타다시 선택투과성 필름
EP1760010A1 (de) * 2005-09-01 2007-03-07 Seminis Vegetable Seeds, Inc. Kunststoffbeutel mit frischen kochfertigen Gemüsen und mit einer Kartusche mit aromatischen Extraktionsteilchen
DE102006024568A1 (de) * 2006-05-23 2007-12-06 Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg Verfahren zur Herstellung einer biologisch abbaubaren Kunststofffolie und Folie
US20110159156A1 (en) * 2009-12-29 2011-06-30 The Garlic Co. Packaged fresh diced garlic and process for making same
US20120164281A1 (en) * 2009-12-29 2012-06-28 The Garlic Co. Packaged fresh diced garlic and process for making same
JP6122687B2 (ja) * 2013-05-01 2017-04-26 積水化学工業株式会社 ポリビニルアルコール溶液、ポリビニルアルコール溶液の製造方法、ポリビニルアルコールフィルムの製造方法及び積層フィルムの製造方法
US20150314979A1 (en) * 2014-05-05 2015-11-05 The Procter & Gamble Company Storage Wrap Material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389695A1 (de) * 1989-03-28 1990-10-03 Neste Oy Gasdichtes Material
EP0454850A1 (de) * 1989-11-20 1991-11-06 Showa Denko Kabushiki Kaisha Polyvinylalkoholcopolymerharzmischung

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US3366592A (en) * 1964-06-24 1968-01-30 Du Pont Polyvinyl alcohol plasticized with 2, 2-diethyl-1, 3-propanediol
US4206101A (en) * 1974-01-03 1980-06-03 E. I. Du Pont De Nemours And Company Melt extrudable cold water-soluble films
DE2603648A1 (de) * 1975-01-31 1976-08-05 Unitika Ltd In wasser loesliche oder dispergierbare aufschmelz-klebstoffmasse und verfahren zu ihrer herstellung
DE2615954C3 (de) 1975-04-22 1981-04-23 Kuraray Co., Ltd., Kurashiki, Okayama Membran auf Basis von Polyvinylalkohol
JPS602404B2 (ja) 1977-06-17 1985-01-21 三菱レイヨン株式会社 アクリル系中空フイラメントの製造方法
CA1230795A (en) * 1981-11-10 1987-12-29 Edward J. Kaufmann Borate solution soluble polyvinyl alcohol films
JPH0717806B2 (ja) * 1986-12-30 1995-03-01 株式会社クラレ 樹脂組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389695A1 (de) * 1989-03-28 1990-10-03 Neste Oy Gasdichtes Material
EP0454850A1 (de) * 1989-11-20 1991-11-06 Showa Denko Kabushiki Kaisha Polyvinylalkoholcopolymerharzmischung

Also Published As

Publication number Publication date
US5270372A (en) 1993-12-14
DE69230086T2 (de) 2000-01-27
AU2050392A (en) 1993-03-11
AU647291B2 (en) 1994-03-17
US5318812A (en) 1994-06-07
DE69230086D1 (de) 1999-11-11
EP0524823A2 (de) 1993-01-27
EP0524823A3 (en) 1993-05-05

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